CN102964454A - Preparation method of nano-cellulose - Google Patents
Preparation method of nano-cellulose Download PDFInfo
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- CN102964454A CN102964454A CN2012104989998A CN201210498999A CN102964454A CN 102964454 A CN102964454 A CN 102964454A CN 2012104989998 A CN2012104989998 A CN 2012104989998A CN 201210498999 A CN201210498999 A CN 201210498999A CN 102964454 A CN102964454 A CN 102964454A
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Abstract
The invention discloses a preparation method of nano-cellulose, comprising the following steps of: firstly, swelling the raw material cellulose by aqueous alkali, soaking for a while, centrifugally separating out cellulose, and washing by deionized water till the filter liquor is neutral; dispersing the separated cellulose in water, adding sodium bromide, 2, 2, 6, 6-tetramethyl piperidine-1-oxide and sodium hypochlorite solution, carrying out an oxidation reaction under sonic oscillation, centrifugally separating after reaction, and carrying out freeze drying treatment on suspension liquid to obtain the nano-cellulose powder. Compared with the prior art, the preparation method is incompact in cellulose structure, can enlarge the unit cell distance, and can improve the reaction accessibility after the raw material cellulose is pretreated, so that the oxidation reaction efficiency can be improved, and the product yield can be obviously improved; the oxidation reaction conditions are mild, and are easy to control, and the product quality can not be influenced due to the fact that only a small quantity of sodium chloride and minute quantity of oxidizing agent are mixed in a reaction system after the reaction; and the sonic oscillation is adopted in the process of reaction, so that the oxidation reaction speed can be accelerated, and the reaction time can be obviously shortened.
Description
Technical field
The present invention relates to a kind of preparation method of nano-cellulose, belong to technical field of nano material.
Background technology
Nano-cellulose is as a kind of natural polymer nano material, have inexpensive, be easy to get, renewable, physiologically acceptable, preparation are simple, can chemistry or the advantage such as physically modified, the aspects such as it is fixed in macromolecule reinforced composite, mould material, biomolecules, optical material all are widely used.
The preparation method of nano-cellulose is generally vitriol oil hydrolysis method, and concentrated acid is by to the hydrolysis of Mierocrystalline cellulose crystallizing field and pars amorpha, isolates purity height, nano-cellulose that degree of crystallinity is complete.Although the method is simple to operate, reaction conditions is easy to control, there are the problems such as aftertreatment technology is complicated, high to the production unit requirement, the reaction acid solution is difficult.For example CN101509209A discloses a kind of preparation method of clubbed nano-cellulose, and employing concentration is that the vitriol oil of 50%-65% is hydrolyzed to cellulosic material, and the hydrolysis acid solution is difficult to process, and the product postprocessing process is complicated, is difficult to operation.
One of approach that Mierocrystalline cellulose is carried out oxide treatment is: with the N-oxycompound as the cellulose oxidation catalyzer, with the coexistence of Sodium Bromide and clorox under cellulosic material is processed, can introduce carboxyl at cellulose macromolecule, N-oxycompound in the reaction process, Sodium Bromide and clorox react the nitrous ion that has generated oxygenizement jointly, thereby the C6 position primary hydroxyl of cellulose surface is oxidized to carboxyl, in oxidising process, also can produce a small amount of nano-cellulose, but because cellulose crystallity is high, it is inner that oxygenant is difficult to enter the Mierocrystalline cellulose crystallizing field, causes the reaction times long.In addition, handled cellulosic material concentration is low, and mass concentration only has about 1%, and production efficiency is very low.CN101903572A discloses a kind of cellulose nano-fibrous manufacture method, at first cellulosic material is carried out oxide treatment, then SURGICEL is carried out the fine processing of the high rotating speed solution of 12000rpm, obtain cellulose nano-fibrous suspension, the method exists separates the fine rotating speed height of processing, energy consumption is high, the problem higher to equipment requirements.Therefore be necessary to seek a kind of environment-friendly high-efficiency, nano-cellulose preparation method simple to operate.
Summary of the invention
The object of the invention is to, a kind of preparation method of nano-cellulose is provided.The present invention passes through the alkali pre-treatment with cellulosic material, and adopts sonic oscillation in oxidation reaction process, so that oxidation time obviously shortens, the nano-cellulose efficiency of pcr product obviously improves.
The technical solution used in the present invention: a kind of preparation method of nano-cellulose may further comprise the steps:
(1) pre-treatment: at ambient temperature, with the aqueous slkali soaking raw cellulose of 5-20 times of raw cellulose quality after 1-30 hour, leach Mierocrystalline cellulose and with deionized water wash, be washed till filtrate pH value and be 6-8;
(2) oxidizing reaction: the Mierocrystalline cellulose that leaches is dispersed in the deionized water of 20-60 times of raw cellulose quality, stir 2 of the lower Sodium Bromide that adds respectively raw cellulose quality 1%-15%, raw cellulose quality 0.001%-2%, 2,6,6-tetramethyl piperidine-1-oxide compound and raw cellulose quality 3-5 mass concentration doubly is 5% chlorine bleach liquor, open simultaneously sonic oscillation, regulating and keep reacting liquid pH value with alkaline solution is 10-11;
(3) aftertreatment: when reacting constant to the pH value, the reaction solution centrifugation is obtained nano-cellulose suspension; Suspension is processed through lyophilize, gets the nano-cellulose powder.
In the preceding method, step (1), (2) described raw cellulose are preferably Microcrystalline Cellulose.
In the preceding method, the used alkaline solution of step (1) pre-treatment is preferably sodium hydroxide or the potassium hydroxide aqueous solution of mass concentration 1%-12%.
In the preceding method, the used alkaline solution of step (2) conditioned reaction liquid pH value is the aqueous sodium hydroxide solution of 0.5mol/L.
In the preceding method, the mass ratio of the described raw cellulose of step (1) and alkaline solution is preferably 1:10-20.
In the preceding method, the described soak time of step (1) is preferably 5-20 hour.
In the preceding method, the add-on of the described Sodium Bromide of step (2) is preferably the 10%-15% of raw cellulose quality, 2,2,6, the 6-tetramethyl piperidine-add-on of 1-oxide compound is preferably the 1%-2% of raw cellulose quality, and chlorine bleach liquor's add-on is preferably 3 times of raw cellulose quality.
In the preceding method, the ultrasonic frequency of the described sonic oscillation of step (2) is 20-50kHz, and ultrasonic power is 100-500w.
In the preceding method, the described centrifugation number of times of step (3) is 2-5 time, and rotating speed is 10000-16000rpm.
The size range of the prepared nano cellulose crystal particle of the present invention is long at 100～200nm, and 10～20nm is wide; The FT-IR spectroscopic analysis shows that there is carboxyl in this nano cellulose crystal surface, and its crystal formation is the cellulose Ⅱ configuration by the cellulose Ⅰ transformation of configuration of raw cellulose; Thermogravimetric analysis is the result show, the thermal stability of the nano cellulose crystal that makes obviously is better than raw cellulose.
Compared with prior art, the present invention has following advantage:
(1) because alkaline solution has swelling action to Mierocrystalline cellulose, thereby after the present invention adopted alkaline solution that raw cellulose is carried out pre-treatment, cellulosic structure was loose, it is large that cell pitch becomes, the reaction accessibility improves, thereby has improved efficiency, and efficiency of pcr product obviously improves.
(2) oxidation reaction condition of preparation nano-cellulose is gentle, is easy to control; And after finishing, reaction only have the oxygenant of a small amount of sodium-chlor and minute quantity to be mingled in the reaction system, on not impact of quality product.
(3) adopt sonic oscillation in the oxidation reaction process, accelerated reaction process; Owing to produce strong cavatition in the ultra-sonic oscillation process, promote the Mierocrystalline cellulose hydrogen bond rupture, thereby accelerate oxidizing reaction speed, greatly saved the reaction times.
Embodiment
Embodiments of the invention 1: the preparation of nano-cellulose:
(1) pre-treatment: at ambient temperature, be that 7% aqueous sodium hydroxide solution soaked 5 gram Microcrystalline Celluloses after 10 hours with 50 gram mass concentration, leach Mierocrystalline cellulose and with deionized water wash, being washed till filtrate pH value is 8.
(2) oxidizing reaction: the Mierocrystalline cellulose that leaches is dispersed in the 100mL deionized water, add respectively 0.5g Sodium Bromide and 0.05g 2,2,6,6-tetramethyl piperidine-1-oxide compound, after being stirred to dissolving, adding 20g mass concentration is 5% chlorine bleach liquor, opens sonic oscillation, ultrasonic power is 300w, frequency is 20kHz, and the aqueous sodium hydroxide solution conditioned reaction liquid potential of hydrogen with 0.5mol/L maintains about 10-11 reacting liquid pH value.
(3) aftertreatment: react to pH value during without considerable change (reaction lasts 150min), with reaction solution centrifugation 3 times, rotating speed 12000rpm removes the large size Mierocrystalline cellulose, and suspension is processed through lyophilize, obtains the nano-cellulose powder.
Embodiments of the invention 2: the preparation of nano-cellulose:
It is in 9% the aqueous sodium hydroxide solution that 5 gram Microcrystalline Celluloses are dispersed in 30 gram mass concentration, soaks at ambient temperature to leach Mierocrystalline cellulose after 15 hours and with deionized water wash, being washed till filtrate pH value is 7.The Mierocrystalline cellulose that leaches is dispersed in the 200mL deionized water, add respectively 0.75g Sodium Bromide and 0.1g 2,2,6,6-tetramethyl piperidine-1-oxide compound, after being stirred to dissolving, adding 25g mass concentration is 5% chlorine bleach liquor, opens sonic oscillation, ultrasonic power is 500w, frequency is 30kHz, and the aqueous sodium hydroxide solution conditioned reaction liquid potential of hydrogen with 0.5mol/L maintains about 10-11 reacting liquid pH value.React to pH value during without considerable change (reaction lasts 85min), with reaction solution centrifugation 4 times, rotating speed 10000rpm removes the large size Mierocrystalline cellulose, and suspension is processed through lyophilize, obtains the nano-cellulose powder.
Embodiments of the invention 3: the preparation of nano-cellulose:
It is in 4% the potassium hydroxide aqueous solution that 5 gram Microcrystalline Celluloses are dispersed in 80 gram mass concentration, soaks at ambient temperature to leach Mierocrystalline cellulose after 20 hours and with deionized water wash, being washed till filtrate pH value is 6.The Mierocrystalline cellulose that leaches is dispersed in the 300mL deionized water, add respectively 0.7g Sodium Bromide and 0.03g 2,2,6,6-tetramethyl piperidine-1-oxide compound, after being stirred to dissolving, adding 15g mass concentration is 5% chlorine bleach liquor, opens sonic oscillation, ultrasonic power is 400w, frequency is 40kHz, and the aqueous sodium hydroxide solution conditioned reaction liquid potential of hydrogen with 0.5mol/L maintains about 10-11 reacting liquid pH value.When reacting constant to the pH value (reaction lasts 115min), with reaction solution centrifugation 2 times, rotating speed 15000rpm removes the large size Mierocrystalline cellulose, and suspension is processed through lyophilize, obtains the nano-cellulose powder.
Comparative example 1:
5 gram Microcrystalline Celluloses are dispersed in the 100mL deionized water, add respectively 0.5g Sodium Bromide and 0.05g 2,2,6,6-tetramethyl piperidine-1-oxide compound, be stirred to dissolving after, adding 20g mass concentration is 5% chlorine bleach liquor, aqueous sodium hydroxide solution conditioned reaction liquid potential of hydrogen with 0.5mol/L maintains about 10-11 reacting liquid pH value, react to the pH value without considerable change till (reaction lasts 300min).With the reaction solution centrifugation, remove the large size Mierocrystalline cellulose, suspension is processed through lyophilize, obtains the nano-cellulose powder.
Comparative example 2:
It is in 7% the aqueous sodium hydroxide solution that 5 gram Microcrystalline Celluloses are dispersed in 50 gram mass concentration, soaks at ambient temperature to leach Mierocrystalline cellulose after 10 hours and with deionized water wash, being washed till filtrate pH value is 8.The Mierocrystalline cellulose that leaches is dispersed in the 100mL deionized water, add respectively 0.5g Sodium Bromide and 0.05g 2,2,6,6-tetramethyl piperidine-1-oxide compound, be stirred to dissolving after, adding 20g mass concentration is 5% chlorine bleach liquor, aqueous sodium hydroxide solution conditioned reaction liquid potential of hydrogen with 0.5mol/L maintains about 10-11 reacting liquid pH value, react to the pH value without considerable change till (reaction lasts 245min).With the reaction solution centrifugation, remove the large size Mierocrystalline cellulose, suspension is processed through lyophilize, obtains the nano-cellulose powder.
The oxidation time of embodiment 1-3 and comparative example 1-2 and nano-cellulose yield all are listed in the table below 1, as can be seen from Table 1, behind cellulosic material process alkali pre-treatment and the ultrasonic booster action, oxidation time obviously shortens, and the nano-cellulose efficiency of pcr product obviously improves.Wherein ultrasonic power is larger on the impact of oxidation time, and power is higher, and the reaction times is shorter.
Table 1
| Ultrasonic frequency | Ultrasonic power | Oxidation time (min) | Nano-cellulose yield (%) | |
| Embodiment 1 | 20kHz | 300w | 150 | 51 |
| Embodiment 2 | 30kHz | 500w | 85 | 46 |
| Embodiment 3 | 40kHz | 400w | 115 | 47 |
| Comparative example 1 | -- | -- | 300 | 12 |
| Comparative example 2 | -- | -- | 245 | 27 |
Claims (9)
1. the preparation method of a nano-cellulose is characterized in that: may further comprise the steps:
(1) pre-treatment: at ambient temperature, with the aqueous slkali soaking raw cellulose of 5-20 times of raw cellulose quality after 1-30 hour, leach Mierocrystalline cellulose and with deionized water wash, be washed till filtrate pH value and be 6-8;
(2) oxidizing reaction: the Mierocrystalline cellulose that leaches is dispersed in the deionized water of 20-60 times of raw cellulose quality, stir 2 of the lower Sodium Bromide that adds respectively raw cellulose quality 1%-15%, raw cellulose quality 0.001%-2%, 2,6,6-tetramethyl piperidine-1-oxide compound and raw cellulose quality 3-5 mass concentration doubly is 5% chlorine bleach liquor, open simultaneously sonic oscillation, regulating and keep reacting liquid pH value with alkaline solution is 10-11;
(3) aftertreatment: when reacting constant to the pH value, the reaction solution centrifugation is obtained nano-cellulose suspension; Suspension is processed through lyophilize, gets the nano-cellulose powder.
2. the preparation method of described nano-cellulose according to claim 1, it is characterized in that: step (1), (2) described raw cellulose are Microcrystalline Cellulose.
3. the preparation method of described nano-cellulose according to claim 1 and 2, it is characterized in that: the used alkaline solution of step (1) pre-treatment is sodium hydroxide or the potassium hydroxide aqueous solution of mass concentration 1%-12%.
4. the preparation method of described nano-cellulose according to claim 1 and 2, it is characterized in that: the used alkaline solution of step (2) conditioned reaction liquid pH value is the aqueous sodium hydroxide solution of 0.5mol/L.
5. the preparation method of described nano-cellulose according to claim 1 and 2, it is characterized in that: the mass ratio of the described raw cellulose of step (1) and alkaline solution is 1:10-20.
6. the preparation method of described nano-cellulose according to claim 1 and 2, it is characterized in that: the described soak time of step (1) is 5-20 hour.
7. the preparation method of described nano-cellulose according to claim 1 and 2, it is characterized in that: the add-on of the described Sodium Bromide of step (2) is the 10%-15% of raw cellulose quality, 2,2,6, the add-on of 6-tetramethyl piperidine-1-oxide compound is the 1%-2% of raw cellulose quality, and chlorine bleach liquor's add-on is 3 times of raw cellulose quality.
8. the preparation method of described nano-cellulose according to claim 1, it is characterized in that: the ultrasonic frequency of the described sonic oscillation of step (2) is 20-50kHz, and ultrasonic power is 100-500w.
9. the preparation method of described nano-cellulose according to claim 8, it is characterized in that: the described centrifugation number of times of step (3) is 2-5 time, and rotating speed is 10000-16000rpm.
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Cited By (22)
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| CN103193889A (en) * | 2013-04-09 | 2013-07-10 | 南京林业大学 | Preparation and separation method of oxidized microcrystalline cellulose |
| CN103255663A (en) * | 2013-05-27 | 2013-08-21 | 江南大学 | Method for improving efficiency of catalytically oxidizing cellulose by tetramethyl piperidine through pre-treatment |
| CN103726378A (en) * | 2013-12-26 | 2014-04-16 | 湖北葛店人福药用辅料有限责任公司 | Method for preparing microcrystalline cellulose at low temperature |
| CN105175557A (en) * | 2015-08-21 | 2015-12-23 | 广西大学 | Preparation method of nano cellulose |
| WO2016055782A1 (en) * | 2014-10-08 | 2016-04-14 | Brunel University | Method of producing nanocellulose |
| CN105568730A (en) * | 2015-12-21 | 2016-05-11 | 同济大学 | Method for preparing renewable nano-celluloses |
| CN105780567A (en) * | 2016-02-02 | 2016-07-20 | 华南理工大学 | Nanometer fiber substrate material for flexible OLED bottom emission and preparation method thereof |
| CN106283209A (en) * | 2016-08-16 | 2017-01-04 | 东华大学 | A kind of method utilizing coir fibre to prepare different scale nanometer fibril and purposes |
| CN106758492A (en) * | 2017-02-21 | 2017-05-31 | 东北农业大学 | A kind of many site oxidizing process prepare method and its application of nano-cellulose |
| TWI613220B (en) * | 2016-07-13 | 2018-02-01 | 臺灣塑膠工業股份有限公司 | Method of producing cellulose nano fiber |
| CN107653723A (en) * | 2017-09-11 | 2018-02-02 | 天津科技大学 | A kind of achievable chemi-mechanical pulp microfibril and the method for strengthening paper physical intensity |
| CN107780273A (en) * | 2017-09-11 | 2018-03-09 | 天津科技大学 | A kind of method for preparing cellulose micro-nano fibril |
| CN109880118A (en) * | 2019-03-04 | 2019-06-14 | 西南石油大学 | Lignin fiber type nanofibrils material, stable foam system based on the material and its preparation method and application |
| CN109972223A (en) * | 2017-12-27 | 2019-07-05 | 台湾塑胶工业股份有限公司 | Cellulose nano-fibrous manufacturing method |
| CN110157160A (en) * | 2018-03-21 | 2019-08-23 | 韩银兰 | A kind of high-performance environmentally-friendly degradable billboard and preparation method thereof |
| CN110590964A (en) * | 2019-10-24 | 2019-12-20 | 福州大学 | Kelp cellulose nanofiber and preparation method thereof |
| CN111116762A (en) * | 2020-01-10 | 2020-05-08 | 天津科技大学 | Preparation method of hydrophobic cellulose nanocrystals |
| CN111944066A (en) * | 2019-05-14 | 2020-11-17 | 中国科学技术大学 | Cellulose-containing biomass material with nano-crystallized surface and preparation method and application thereof |
| CN112679258A (en) * | 2020-12-24 | 2021-04-20 | 广东金正大生态工程有限公司 | Composite microbial fertilizer and preparation method thereof |
| CN113832765A (en) * | 2021-10-25 | 2021-12-24 | 西北大学 | Preparation method of 3D (three-dimensional) reticular high-crystallinity walnut shell-based nanocellulose |
| CN114318923A (en) * | 2021-04-30 | 2022-04-12 | 西北大学 | Method for preparing high-crystallinity three-dimensional reticular nano-cellulose based on amygdalus pedunculata pall shells |
| CN115467156A (en) * | 2022-09-28 | 2022-12-13 | 郑州大学 | Test tube brush-shaped plant fiber and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690358A (en) * | 2012-06-01 | 2012-09-26 | 南京信息工程大学 | Cellulose nanocrystal suspension and preparation method thereof |
-
2012
- 2012-11-29 CN CN201210498999.8A patent/CN102964454B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690358A (en) * | 2012-06-01 | 2012-09-26 | 南京信息工程大学 | Cellulose nanocrystal suspension and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘鹤: "纤维素纳米晶体及其复合物的制备与应用研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》, 15 March 2012 (2012-03-15) * |
| 覃忠严: "超声波协同TEMPO氧化法制备纳米纤维微晶的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, 15 May 2012 (2012-05-15) * |
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| CN103255663A (en) * | 2013-05-27 | 2013-08-21 | 江南大学 | Method for improving efficiency of catalytically oxidizing cellulose by tetramethyl piperidine through pre-treatment |
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| CN111116762A (en) * | 2020-01-10 | 2020-05-08 | 天津科技大学 | Preparation method of hydrophobic cellulose nanocrystals |
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| CN112679258A (en) * | 2020-12-24 | 2021-04-20 | 广东金正大生态工程有限公司 | Composite microbial fertilizer and preparation method thereof |
| CN114318923A (en) * | 2021-04-30 | 2022-04-12 | 西北大学 | Method for preparing high-crystallinity three-dimensional reticular nano-cellulose based on amygdalus pedunculata pall shells |
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| CN115467156A (en) * | 2022-09-28 | 2022-12-13 | 郑州大学 | Test tube brush-shaped plant fiber and preparation method and application thereof |
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